WO2013100734A1 - Procédé de fabrication d'un film de zéolite dans lequel un axe est orienté complètement verticalement, à l'aide de vapeur d'eau dans des conditions exemptes de gel synthétique - Google Patents

Procédé de fabrication d'un film de zéolite dans lequel un axe est orienté complètement verticalement, à l'aide de vapeur d'eau dans des conditions exemptes de gel synthétique Download PDF

Info

Publication number
WO2013100734A1
WO2013100734A1 PCT/KR2012/011807 KR2012011807W WO2013100734A1 WO 2013100734 A1 WO2013100734 A1 WO 2013100734A1 KR 2012011807 W KR2012011807 W KR 2012011807W WO 2013100734 A1 WO2013100734 A1 WO 2013100734A1
Authority
WO
WIPO (PCT)
Prior art keywords
seed crystals
film
axis
substrate
porous substrate
Prior art date
Application number
PCT/KR2012/011807
Other languages
English (en)
Korean (ko)
Inventor
윤경병
탄 툼 팜카오
Original Assignee
서강대학교산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 서강대학교산학협력단 filed Critical 서강대학교산학협력단
Priority to US14/369,973 priority Critical patent/US9938637B2/en
Publication of WO2013100734A1 publication Critical patent/WO2013100734A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B19/00—Liquid-phase epitaxial-layer growth
    • C30B19/12—Liquid-phase epitaxial-layer growth characterised by the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
    • C04B38/0025—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors starting from inorganic materials only, e.g. metal foam; Lanxide type products
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/34—Silicates
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/528—Spheres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]

Definitions

  • the present invention relates to a method for preparing a zeolite-based membrane using secondary growth in steam without a gel-type silicon source.
  • Zeolite is generically referred to as crystalline aluminosilicate. Since the site of aluminum in the skeleton of the aluminosilicate is negatively charged, positive ions exist in the pores and the remaining space in the pores is usually filled with water molecules. The structure, shape, and size of the three-dimensional pores of the zeolite depend on the type of zeolite, but the diameter of the pores usually corresponds to the molecular size. Therefore, zeolites are also called molecular sieves because they have the size selectivity or shape selectivity of the molecules to be taken into the pores depending on the kind.
  • zeotype molecular sieves are known in which a part or all of silicon or aluminum is replaced by various other elements instead of silicon (Si) and aluminum (Al), which constitute the skeletal structure of the zeolite.
  • porous silica sicalite
  • AlPO 4 alpo
  • Ti, Mn, Co, Fe in the skeleton of such zeolite and pseudomolecular sieves
  • pseudomolecules obtained by partially substituting various metal elements such as Zn.
  • zeolite in the present specification means a zeolite having a broad meaning including the above-described pseudomolecular body.
  • zeolites having an MFI structure are among the most actively used zeolites, and their kinds are as follows:
  • ZSM-5 A zeolite of MFI structure in which silicon and aluminum are formed in a constant ratio.
  • Silicalite-1 Zeolite having a structure composed only of silica.
  • TS-1 Zeolite of MFI structure with titanium (Ti) in some aluminum spots.
  • the MFI structure is shown in FIG.
  • a channel in which the elliptical (0.51 ⁇ 0.55 nm) pores are zigzag-shaped flows in the a-axis direction, and pores close to the circular (0.54 ⁇ 0.56 nm) form a straight line and extend in the b-axis direction to form a straight channel.
  • the channel is not open in the c-axis direction.
  • Powdered MFI zeolites are widely used in real life and industry as cracking catalysts, adsorbents, dehydrating agents, ion exchangers, and gas purifiers of crude oil, but MFI zeolite thin films formed on porous substrates such as porous alumina It is widely used as a molecular separation membrane that can be separated according to.
  • MFI zeolite thin films are secondary and tertiary nonlinear optical films, three-dimensional memory materials, solar collectors, electrode aids, semiconductor quantum dots and quantum wire carriers, molecular circuits, photosensitive devices, emitters, low dielectric films (low dielectric thin film or low k thin film) and antirust coatings.
  • the shape, size and channel structure of the pores differ depending on the crystal direction.
  • a method of producing a zeolite thin film of MFI structure on a substrate such as a glass plate is divided into primary growth method (primary growth method) and secondary growth method (secondary growth method).
  • first growth method the substrate is placed in an MFI zeolite synthesis gel without pretreatment, and the MFI zeolite membrane is spontaneously grown on the substrate.
  • the gel for synthesis is usually a structure added with a structure directing agent or an organic template (organic template) added to the tetrapropyl ammonium hydroxide (referred to as tetraproplyammonium hydroxide, TPAOH).
  • the MFI crystals grow on the glass plate placed at the initial stage of the reaction in a direction perpendicular to the glass plate.
  • crystals oriented in the a-axis begin to grow parasitically.
  • crystals grow in various directions, resulting in thin films in various orientations.
  • the resulting MFI zeolite thin films with random orientation have their own uses but poor applicability.
  • the permeability (molecular permeability) of one of the most important factors when applied as a molecular separation membrane is significantly reduced.
  • the MFI zeolite thin film does not grow on the substrate. To overcome this problem, the secondary growth method is used.
  • the substrate to which the MFI zeolite crystals are previously attached is immersed in the MFI synthetic gel and then reacted to form an MFI thin film.
  • already attached MFI crystals serve as seed crystals.
  • the orientation of the pre-attached MFI zeolite crystal plays a very important role in the orientation of the MFI zeolite thin film formed later.
  • the a-axis of the MFI zeolite seed crystals is oriented perpendicular to the substrate
  • the a-axis of the resulting MFI zeolite thin film tends to be oriented in a direction perpendicular to the substrate and later generated if the b-axis of the seed crystals is oriented perpendicular to the substrate.
  • the b-axis of the MFI zeolite thin film is oriented in the direction perpendicular to the substrate.
  • the orientation of the resulting zeolite thin film is sensitively dependent on the structure inducing agent added to the MFI synthetic gels put in to form the thin film, rather than the orientation of the seed crystals.
  • TPAOH has usually been added to MFI synthetic gels that have been used in secondary growth methods. In this case, even though the orientations of the attached MFI zeolite seed crystals are all attached so that the a-axis or the b-axis is perpendicular to the substrate, the orientation of the finally produced MFI zeolite thin film changes randomly.
  • Another object of the present invention is to provide a film in which the crystallographic orientation of seed crystals aligned on a substrate is maintained.
  • the present invention provides a membrane produced by the above production method.
  • the present invention is characterized by using a porous substrate capable of supplying silicon instead of using a synthetic gel as a silicon source in the secondary growth method.
  • the material that can supply silicon in the porous substrate is not particularly limited as long as it can supply silicon (Si), but it is preferable that it is porous as an amorphous material, and non-limiting examples include oxides containing silicon and having hydroxy groups on the surface thereof.
  • porous silica is more preferred.
  • a non-limiting example of a porous substrate capable of supplying silicon may be a molding in which silica particles, preferably amorphous silica particles are filled into a mold and then compressed. This is because the substrate, which is porous and formed of amorphous particles, has a low crystallinity and can readily dissolve silicon. For the same reason, the larger the porosity is, the more preferable the porous substrate is.
  • amorphous silica oxide film when an amorphous silica oxide film is formed on a surface, it is preferable as a porous base material which can supply silicon. In silicon wafers, amorphous silica oxide films are better formed in steam.
  • the seed crystals used by the present invention and the skeletal component of the formed film are not particularly limited as long as they contain silicon.
  • Seed crystals and the formed film may be zeolites or similar molecular sieves.
  • the seed crystals and the formed film may be MFI structure.
  • zeolite refers not only to (i) a generic term for minerals that are aluminum silicate hydrates of alkali or alkaline earth metals, but also to (ii) various elements in place of silicon (Si) and aluminum (Al), which are the elements that make up the zeolite skeleton structure. It also includes zeotype molecular sieves that have replaced some or all of silicon or aluminum as an element, and in the larger sense includes all porous oxides or sulfides having hydroxyl groups on the surface.
  • zeolite or pseudomolecular sieves of MFI structure examples include ZSM-5, silicalite, TS-1, AZ-1, Bor-C, Boralite C, encilite, FZ-1, LZ-105, monoclinic H-ZSM -5, mutinite, NU-4, NU-5, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B and the like.
  • the material capable of supplying silicon in the seed crystals and the porous substrate is the same material, and it is preferable that both are SiO 2 .
  • Seed crystals are preferably ordered porous materials.
  • the size of the seed crystals is larger than the pores and pores of the porous substrate so that some or all of the seed crystals protrude above the surface of the porous substrate, so that the seed crystals can function as seed crystals in the manufacturing method of the present invention and thereafter grow secondary.
  • a film can be formed by the method (FIG. 12).
  • the size of the seed crystal is larger than the pores and pores of the porous substrate so that the seed crystal can be laid flat on the surface of the porous substrate so that at least one crystal axis of the seed crystal can be oriented in a specific direction, from which at least one crystal axis The secondary film oriented in this specific direction can be formed (FIG. 11).
  • the relationship between the crystal axis a, the b axis, and the c axis is that the crystal axis c axis does not exist on the plane formed by the crystal axis a axis and the b axis.
  • the crystal axes a, b, and c axes may be perpendicular to each other, or the crystal axes c axis may be inclined on a plane formed by the crystal axes a and b axes.
  • the present invention provides a template for secondary growth when forming and growing a film from seed crystals attached on a substrate by a secondary growth method, the crystal axis a-axis of each anisotropic seed crystal on the substrate, At least one or both of the b-axis and c-axis may be aligned to be oriented on the porous substrate according to certain rules.
  • seed crystals aligned on a substrate may be oriented according to whether all a axes of the seed crystals are parallel to each other, all b axes of the seed crystals are parallel to each other, all c axes of the seed crystals are parallel, or a combination thereof. It may be.
  • the seed crystals aligned on the substrate may be a axis, b axis or c axis oriented perpendicular to the substrate surface.
  • seed crystals on which one or more or all of the a-axis, the b-axis, and the c-axis are oriented in accordance with a certain rule form a monolayer.
  • seed crystals may form two dimensional interconnections with each other and / or seed crystals grow perpendicular to the substrate surface to form a single crystal film that is larger than a single seed crystal and all crystal axis orientations are identical.
  • the size of the seed crystals may be nm 3 ⁇ um 3 scale (scale)
  • the two-dimensional size of the film thus formed may be mm 2 ⁇ cm 2 and the thickness of the film can be continuously increased, so that the grown single crystal film Three-dimensional size is also available in ⁇ cm 3 scale.
  • the non-spherical seed crystals aligned on the substrate in the present invention are aligned so that all of the crystal axes a, b and c axes are aligned according to a certain rule, the non-spherical seed crystals may have the same or different shapes. .
  • Korean Patent Publication No. 2009-120846 discloses a method of vertically orienting all b-axis of MFI type seed crystals on a substrate, and is capable of adjusting the a-axis, b-axis and / or c-axis orientation of the crystals on the substrate.
  • the technique is described in PCT / KR2010 / 002180 and PCT / KR2010 / 002181.
  • seed crystals aligned on at least one or both of the a-axis, b-axis and c-axis orientations on the substrate may be prepared according to the methods described in Korean Patent Publication Nos. 2009-120846, PCT / KR2010 / 002180 and PCT / KR2010 / 002181 or We can prepare by application.
  • seed crystals in which the a-axis, b-axis, and c-axis orientations are all aligned on the substrate may be prepared by the following process:
  • the shape of the pore is preferably formed to correspond to the shape of a predetermined portion of the seed crystal inserted into the pore in order to adjust the crystal axis orientation of the seed crystal.
  • Physical pressure may be applied by rubbing or pressing against substrate.
  • the intaglio or embossment formed on the substrate or mold substrate surface may be directly imprinted on the substrate itself, formed by photoresist, formed by laser ablation after coating the sacrificial layer, or formed by inkjet printing.
  • the photoresist or ink may be removed after aligning the seed crystals on the substrate, but may continue to be a support for seed crystals, even during secondary growth, as long as they do not cause problems with the supply of silicon and structure inducing agents to the seed crystals. .
  • seed crystals inserted into the pores on the substrate or the mold substrate may gather to form a specific pattern or shape, and a film formed corresponding thereto may also form a specific pattern or shape.
  • a coupling agent capable of binding to the substrate and seed crystals may be applied on the substrate surface.
  • the term "linker” refers to any compound having a functional group at the terminus that enables binding between the substrate and seed crystals. Preferred linking agents and mechanisms of action and applications thereof are disclosed in Korean Patent Publication Nos. 2009-120846 and US 7,357,836.
  • the present invention uses a porous substrate containing a material capable of supplying silicon to a silicon source when producing a film by the secondary growth method, it does not require a silicon source in the form of a gel and provides a structure inducing agent as an aqueous solution rather than a gel. to be.
  • the structure inducing agent is a material that serves as a template of a specific crystalline structure, and the charge distribution, size, and geometric shape of the structure inducing agent provide structure directing properties.
  • the structure inducing agent used in the present invention is preferably a kind which induces only secondary growth from the surface of the seed crystals and does not induce crystal nucleation in the seed crystal growth solution or at the seed crystal surface. Unless only crystal nucleation is induced, the rate of crystal growth along each crystal axis is not critical.
  • Seed crystals used in the second step can also be formed using a seed structure directing agent. Since seed structure inducing agents induce crystal nucleation reactions, it is not preferable to use seed structure inducing agents as structure inducing agents for secondary growth methods. Therefore, the structure inducing agent (SDA) used in the third step is preferably different from the seed structure inducing agent.
  • SDA structure inducing agent
  • the structural inducer for secondary growth is tetrapropylammonium hydroxide (TPAOH), tetraethylammonium hydroxide (TEAOH), tetramethylammonium (TMA), tetrabutylammonium (TBA) ) Or mixtures thereof. Especially preferred are mixtures of TPAOH and TEAOH.
  • the non-limiting concentration range of the structural inducing agent in the aqueous solution is 0.01 mol to 1 mol, preferably 0.1 mol to 0.5 mol.
  • FIG. 8 is a graph of silicalite-1 seed crystals in which the b-axis is vertically oriented on a silica (SiO 2 ) porous substrate by steam heating reaction at 190 ° C. for 48 hours using various concentrations of aqueous TEAOH-containing solution.
  • SiO 2 silica
  • Non-limiting examples of the method of coating the structure inducing agent-containing aqueous solution on the porous substrate to which the seed crystals are applied include slip-coating spin coating, spray coating, and the slip coating method is preferable (FIG. 5).
  • the substrate is immersed in the aqueous solution containing the structure inducing agent for the surface to which the seed crystals are applied for slip-coating so that only the surface is impregnated, and then the substrate is taken out and the aqueous solution impregnated to the seed crystals is turned upward. May be directed towards the porous substrate.
  • Coating the aqueous solution containing the structure inducing agent on the porous substrate to which the seed crystals are applied may be repeated two or more times.
  • seed crystals are connected to each other two-dimensionally by the second growth from the seed crystal surface to form three-dimensional vertical growth to form a film.
  • the porous substrate impregnated with the coating solution containing the structure inducing agent When the porous substrate impregnated with the coating solution containing the structure inducing agent is heated in a high pressure reactor, the moisture in the porous substrate becomes vapor and transports the silicon and the structure inducing agent from the porous substrate to the seed crystals through the pores. This makes it possible to form a film.
  • the moisture in the porous substrate can also form steam sufficiently.
  • Membrane manufacturing method can be supplied from the porous substrate without the use of a synthetic gel and can provide a structure inducing agent for secondary growth in the form of a solution to reduce unnecessary raw material consumption and synthetic gel is not wasted There is no need to dry and wash the film formed from the seed crystals.
  • the reaction temperature for film formation and growth may vary from 50-250 ° C. depending on the composition of the structure inducing agent aqueous solution used or the material to be made.
  • the reaction temperature is 80-200 ⁇ , more preferably 180-190 ⁇ .
  • the reaction temperature is not always fixed, but can be reacted by changing the temperature in several steps.
  • the reaction time for film formation and growth can vary from 0.5 hours to 20 days.
  • the reaction time is preferably 2 hours-15 days, more preferably 40 to 50 hours.
  • the description of a single seed crystal is achieved by the seed crystals being connected two-dimensionally to each other by the secondary growth from the surface of the seed crystals in the same compartment with all the crystal axis orientations of adjacent seed crystals.
  • Single crystals larger than the maximum diameter parallel to the plane and all crystal axis orientations are identical;
  • the seed crystals grow perpendicular to the substrate surface and form a single crystal with all crystal axis orientations equal to greater than the maximum diameter perpendicular to the substrate surface of the single seed crystal;
  • a crystal can be formed that satisfies both conditions.
  • the film formed in the same crystal axis orientation of adjacent seed crystals may extend to the film in which the channel of the seed crystals is formed.
  • a film formed in a partition having the same crystal axis orientation of adjacent seed crystals may be expanded by continuously connecting channels in an axial direction parallel to the substrate surface; Channels are continuously connected and extended in an axial direction perpendicular to or inclined to the substrate surface; Or both conditions can be satisfied.
  • Membranes prepared according to the present invention are molecular separation membranes, low dielectric materials in the semiconductor industry, nonlinear optical materials, thin films for water decomposition devices, thin films for solar cells, optical components, interior or exterior components for aircrafts, cosmetic containers, living containers, mirrors And other zeolites may be used in a variety of applications, such as thin film using the nanopore characteristics, but is not limited thereto.
  • the film production method according to the present invention consists of a simple manufacturing process, which has high reproducibility and high throughput.
  • the membrane production method according to the present invention can produce a membrane in which the crystal axis orientation of the seed crystals aligned on the porous substrate is maintained.
  • the present invention can form a film in which the channel is formed in the horizontal direction as well as perpendicular to the substrate surface, the film containing a variety of functional molecules, polymers, metal nanoparticles, semiconductor quantum dots, quantum wires, etc. in the nanochannel in a constant orientation for various optical applications It can be used as advanced materials for electronics and electro-optics.
  • a channel is formed in a vertical direction in a membrane formed of porous alumina, porous silica, or mesoporous material, it functions as a separator that separates molecules.
  • FIG. 1 is a view schematically showing the determination of the MFI structure in which a structure inducing agent is inserted.
  • FIG. 2 shows SEM images of anisotropic Coffin type Silicalite-1 crystals and anisotropic Leaf type Silicalite-1 crystals and their crystal axes.
  • the left SEM image is a Coffin type Silicalite-1 crystal and the right SEM image is an anisotropic Leaf type Silicalite-1 crystal.
  • FIG. 3 is an electron micrograph of a glass plate with Silicalite-1 seed crystals attached using a rubbing method (Korean Patent No. 0789661) (image seen from above), wherein the seed seeds attached are oriented such that the b axis is perpendicular to the substrate. But the a and c axes are randomly oriented.
  • FIG. 4 is an SEM image of a silicon wafer in which fine pattern engraving is formed with photoresist (PR) so that seed crystals can be vertically inserted in each of the a-axis, b-axis, and c-axis directions while aligning all crystal axis orientations equally.
  • PR photoresist
  • FIG. 5 is a schematic diagram illustrating a process diagram of a film production method according to one embodiment of the present invention.
  • FIG. 6A is a SEM photograph of a crystal monolayer of silicalite-1 particles with the b-axis perpendicular to the substrate on a SiO 2 porous substrate and an XRD pattern thereof.
  • FIG. 6B is a SEM photograph of the thin film grown secondly according to one embodiment of the present invention using a porous substrate having a silicalite-1 crystal monolayer of FIG. 6A and an XRD pattern thereof.
  • FIG. 7 is a time at 190 ° C. using an aqueous solution containing TPAOH from silicalite-1 seed crystals with the b-axis vertically oriented on a silica (SiO 2 ) porous substrate according to one embodiment of the invention as in FIG. 6B. SEM picture of the film grown second by steam heating reaction.
  • FIG. 8 shows silica b-1 seed crystals vertically oriented on a silica (SiO 2 ) porous substrate by steam heating reaction at 190 ° C. for 48 hours using various concentrations of aqueous solution containing TEAOH. SEM photograph of the second grown film.
  • silicalite-1 seed crystals oriented vertically on the silica (SiO 2 ) porous substrate by steaming reaction over time at 190 ° C. using an aqueous solution containing TPAOH and TEAOH. SEM image of the tea grown film.
  • FIG. 10 is a steaming reaction for 48 hours at 190 ° C. using an aqueous solution containing TPAOH and TEAOH from silicalite-1 seed crystals with b-axis vertically oriented on glass substrate A and silicon wafer B.
  • FIG. 11 shows a silicalite membrane obtained by secondary growth of 800 nm-sized silicalite nanoparticles (A) on a silica (SiO 2 ) porous substrate (surface particle size 500-600 nm) by steam heating at 190 ° C. for various reaction times.
  • the structural inducing agent used at this time is an aqueous solution containing TPAOH and TEAOH.
  • the size of the seed crystals is similar in size to the surface particle size that forms the porous substrate surface, resulting in a secondary film with randomly oriented crystal axes. Therefore, the seed crystals can be laid flat on the porous substrate only when the average grain diameter of the seed crystals is 2 to 3 ⁇ m, so that at least one crystal axis of the seed crystals can be oriented in a direction perpendicular to the substrate, from which at least one A secondary film can be formed in which the crystal axis is oriented perpendicular to the substrate.
  • FIG. 12 (A) is a SEM photograph of a silica porous substrate (surface particle size 500 ⁇ 600nm), (B) is a SEM photograph after rubbing 70 nm size SiO 2 beads to make a smooth surface, (C) is SEM image of the membrane secondarily grown by steam heating at 190 ° C. and for 48 hours using TEAOH and TPAOH containing aqueous solution, (D) is the XRD pattern of the membrane of (C). It was confirmed from (D) that no new crystals were formed.
  • FIG. 13 is a reaction time when a zeolite-based membrane was prepared using a secondary growth method in a steam at 190 ° C. without using a source of gel in the form of a gel in accordance with the present invention using different structure inducing agents (TEAOH, TPAOH + TEAOH, TPAOH).
  • TEAOH, TPAOH + TEAOH, TPAOH different structure inducing agents
  • Void area% means the part where zeolite is not located on the substrate, and when the aqueous solution containing the TPAOH structure inducing agent is used, the zeolite membrane grows fastest, and the zeolite membrane grows in the order using the aqueous solution containing TPAOH + TEAOH and TEAOH structure inducing agent. .
  • the left picture of FIG. 14 is a randomly grown MFI zeolite thin film manufactured by a method of growing a zeolite membrane using an MFI synthetic gel, which is a conventional method, and a gap is generated in a firing step for removing TPAOH during the manufacturing process. It can be confirmed by observing the phosphor between the gaps.
  • the picture on the right is a film in which the crystal axis orientation is kept constant by the method without using the synthetic gel of the present invention. Apochromat 20x / 0.8 M27, Zoom: 1.0, Mater gain: 585, Laser: 488 nm, 2.6% observed).
  • FIG. 15 shows that a zeolite thin film in which all of its axial directions are vertically aligned can be grown to a thin film of 200 nm using steam under conditions without a synthetic gel prepared by the method of the present invention.
  • FIG. 16 is a porous substrate capable of supplying the silicon of the present invention, when zeolite seed crystals are applied to a molded product in which amorphous silica particles are packed into a mold and then compacted, and secondly grown using an aqueous solution containing a TPAOH structure inducing agent.
  • the SEM image shows the growth of the film from the side.
  • FIG. 17 is a porous substrate capable of supplying the silicon of the present invention, when the zeolite seed crystals are placed on a compacted product after filling the mold with 50 nm SiO 2 silica beads, and after the second growth by steam reaction, the silica beads are steamed. SEM photographs show that silicon crystals are supplied to seed crystals as they are etched during the reaction.
  • FIG. 18 is a SEM photograph showing the secondary growth of the SL film on the silica particle support by steam reaction using an aqueous solution containing a TPAOH + TEAOH structure inducing agent according to different reaction time and reaction temperature (a) 160 °C- 8 h (b) 175 ° C-8 h (c) 190 ° C-8 h (d) 190 ° C-18 h. Scale bar represents 5 ⁇ m.
  • 19 is a SEM photograph showing the secondary growth of the SL film on the silica particle support by steam reaction using an aqueous solution containing a TPAOH structure inducer according to different reaction time and reaction temperature (a) 160 °C-8 h (b) 175 ° C-8 h (c) 190 ° C-8 h (d) 190 ° C-18 h. Scale bar represents 5 ⁇ m.
  • FIG. 20 is steam at 190 ° C. for 48 h using various concentrations of aqueous solution containing TEAOH structure inducer (0.01 M (a), 0.02 M (b), 0.04 M (c), 0.05 M (d)) on silica particle supports. SEM pictures showing the secondary growth of the SL film through the reaction is shown.
  • FIG. 21 shows a 48 ° C steam reaction for 48 h using an aqueous solution containing TPAOH + TEAOH structure inducer on (a) a glass support (b) on a cleaned Silicon wafer and (c) a silicon wafer coated with an amorphous SiO 2 layer. SEM image showing the second grown SL film is shown. Scale bar represents 5 ⁇ m.
  • Platinum / palladium coating was performed on the resulting thin film with a thickness of about 15 nm and SEM images were obtained by using a scanning electron microscope (Hitachi S-4300 FE-SEM).
  • an X-ray powder diffraction pattern was prepared using an X-ray diffractometer (Rigaku diffractometer D / MAX-1C, Rigaku) using CuK ⁇ X-rays. Got it.
  • TEAOH 35% Alfa
  • TPAOH 1M Sigma-Aldrich
  • (NH 4 ) 2 SiF 6 98% Sigma-Aldrich
  • Tetraethylorthosilicate-TEOS 98% (Acros-Organic).
  • Example 1-1 Anisotropic, Coffin Type Silicalite-1 Crystals
  • a gel was prepared by adding 22.5 g of TEOS to a PP bottle containing 247.7 mL of DDW, 22.5 mL of TPAOH, and 37.2 g of ethylene glycol (EG). The mixture was stirred for 24 hours to form a clear gel, then 6.168 mL of TEAOH was added and stirred for 12 hours. The resulting transparent gel had a final molar composition of 1 TEOS / 0.15 TPAOH / 0.1 TEAOH / 4 EtOH / 100 H 2 O / 4 EG. After aging, the gel was filtered through No. 2, Whatman filter paper and transferred to a Teflon line autoclave with a clean stirring bar.
  • Example 1-2 Anisotropic Leaf Type Silicalite-1 Crystals
  • a transparent gel was prepared by adding 1.696 g of TEOS to a PP bottle containing Trimer-TPA 3 + -3I - 1.019 g, 0.295 g KOH and 34.2 g DDW.
  • Aged for 24 hours, the gel was filtered through No. 2, Whatman filter paper and transferred to a Teflon line autoclave. The hydrothermal reaction was carried out at 175 ° C. for 24 hours. The product was collected, washed with a large amount of DDW and dried at 100 ° C. for 24 hours to obtain leaf type Silicalite-1 powder (see FIG. 2).
  • Porous silica substrates were prepared using silica particles of 50 to 550 nm size synthesized according to the Stober method (W. Stober et al. J. Colloid Interface Sci. 26, 62 1968):
  • both sides of the porous silica disk were polished with SiC sandpaper (Presi, grit size P800). Both surfaces of the porous silica disk were repolished with SiC sandpaper (Presi, grit size P1200) to smooth the surface.
  • the diameter and thickness of the porous silica disks were 20 mm and 3 mm, respectively.
  • the porosity measured by mercury porosimetry was 45.5% with an average pore size of 250 nm.
  • One drop of DDW was added dropwise onto the porous silica disk.
  • 70 nm of silica car beads were prepared and sintered at 550 ° C. for 24 hours.
  • Sintered 70 nm silica beads were gently rubbed on the porous silica disk until the surface was glazed, filling large gaps in the porous silica substrate made at 350 nm.
  • the resultant smooth porous silica substrate was dried overnight at room temperature and sintered at 550 ° C. for 8 hours in a muffle furnace. The temperature was increased to 550 ° C. for 8 hours and cooled to room temperature for 4 hours.
  • An acetone solution of epoxy resin (10 wt%) was spincoated on a porous silica substrate at 3,000 rpm for 15 seconds and cured at 80 ° C. for 30 minutes.
  • the epoxy coating is intended to prevent the seed crystals from randomly tilting due to gaps in the porous substrate surface when later attempting to mount the seed crystals on the porous substrate surface in a particular orientation.
  • An ethanol solution of polyethyleneimine (PEI, 0.1 wt%) was spin-coated on an epoxy-coated porous silica substrate at a spin rate of 2,500 rpm for 15 seconds.
  • Silicalite crystals (1.0 ⁇ 0.5 ⁇ 1.4 ⁇ m 3 ) were placed on the porous silica substrate and rubbed with a finger so that the silicalite crystals were aligned in a monolayer on the porous substrate (FIG. 6A).
  • the silicalite crystal monolayer supported on the porous silica substrate is denoted SLM / p-SiO 2 .
  • the sintered SLM / p-SiO 2 plate was allowed to stand overnight in a constant humidity chamber to allow the substrate to absorb H 2 O. In order to ensure good vapor formation from the porous substrate later.
  • the hydrated SLM / p-SiO 2 plate was immersed in an aqueous NH 4 F solution (0.2 M) for 5 hours. In order to remove the fine powder from the seed crystals by the rubbing.
  • NH 4 F-treated SLM / p-SiO 2 plates were immersed in fresh DDW for 1 hour and dried at room temperature for 24 hours.
  • Example 4 Film formation and growth by secondary growth from perfectly b-axis aligned silicalite seed crystals
  • aqueous solution of TEAOH aqueous solution of TEAOH, a mixed aqueous solution of TPAOH and TEAOH, and an aqueous solution of TPAOH were used.
  • the SLM / p-SiO 2 plate was coated by the slip-coating process with the structure inducing agent as follows (see FIG. 5): The clean SLM / p-SiO 2 plate was lightly contacted with the structure inducing agent solution. At this time, only one half of the thickness of the porous silica substrate was immersed in the structure inducing agent solution with the silicalite monolayer face down. After soaking for 10-20 seconds, the SLM / p-SiO 2 plate was slowly lifted up. This process was repeated three times. After coating with the structural inducer, the SLM / p-SiO 2 plates were kept at room temperature for 5 seconds in a Petri dish to remove excess water.
  • the SLM / p-SiO 2 plate coated with the structural inducer was transferred to the autoclave of the Teflon line with the silicalite monolayer facing upwards. Secondary growth reactions were carried out without the addition of synthetic gels or water. The closed autoclave was placed in a preheated oven. The reaction was carried out at 160-190 ° C. temperature for 18-48 hours. After a predetermined reaction time, the high pressure reactor was placed in tap water and cooled.
  • the membrane was taken out and left at room temperature for 6-12 hours. Sintering at 440 ° C. for 8 hours in air removes the structure inducing agent. At this time, the heating rate was 60 °C / h and the cooling rate was 90 °C / h.
  • the zeolite thin film could be prepared as a 200 nm thin film by controlling the reaction time and temperature in the preparation step (FIG. 15).
  • a fluorescence microscope (Plan-Apochromat 20x / 0.8 M27, Zoom: 1.0, Mater gain: 585) was prepared by randomly growing MFI zeolite thin films prepared by growing zeolite using MFI synthetic gel. , Laser: 488 nm, observed at 2.6%). Fluorescence was observed between the gaps as a gap was generated in the firing step for removing TPAOH in the manufacturing process during the conventional method.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Structural Engineering (AREA)
  • Metallurgy (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne un procédé de préparation d'un film mince ou d'un film épais, comprenant : une première étape consistant à se procurer un substrat poreux apte à fournir du silicium ; une deuxième étape d'application de cristaux d'ensemencement de zéolite sur la surface du substrat poreux ; une troisième étape de revêtement du substrat poreux à cristaux d'ensemencement appliqués par une solution aqueuse contenant un agent d'orientation de la structure ; et une quatrième étape de formation et de croissance d'un film à partir des cristaux d'ensemencement à l'aide d'un procédé de croissance secondaire au-dessus d'une température à laquelle l'humidité à l'intérieur du substrat poreux à cristaux d'ensemencement appliqués préparé dans la troisième étape peut former de la vapeur d'eau. L'invention concerne également un film préparé par le procédé. Conformément à la présente invention, le procédé de préparation d'un film comprend de simples procédés de fabrication et a ainsi une reproductibilité élevée et un débit élevé. Etant donné qu'un gel synthétique n'est pas utilisé et qu'une solution est utilisée, il est possible de réduire la consommation non nécessaire de matières, la pollution environnementale est diminuée, un gel synthétique n'est pas gaspillé et le séchage et le lavage d'un film ne sont pas nécessaires.
PCT/KR2012/011807 2011-12-30 2012-12-28 Procédé de fabrication d'un film de zéolite dans lequel un axe est orienté complètement verticalement, à l'aide de vapeur d'eau dans des conditions exemptes de gel synthétique WO2013100734A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/369,973 US9938637B2 (en) 2011-12-30 2012-12-28 Production method of zeolite film in which one axis is completely vertically oriented, using steam under synthetic gel-free condition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2011-0147688 2011-12-30
KR20110147688 2011-12-30

Publications (1)

Publication Number Publication Date
WO2013100734A1 true WO2013100734A1 (fr) 2013-07-04

Family

ID=48698058

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2012/011807 WO2013100734A1 (fr) 2011-12-30 2012-12-28 Procédé de fabrication d'un film de zéolite dans lequel un axe est orienté complètement verticalement, à l'aide de vapeur d'eau dans des conditions exemptes de gel synthétique

Country Status (3)

Country Link
US (1) US9938637B2 (fr)
KR (1) KR101421357B1 (fr)
WO (1) WO2013100734A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110882715A (zh) * 2018-09-07 2020-03-17 中国科学院大连化学物理研究所 一种分子筛催化剂的制备方法及应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110963499B (zh) * 2019-12-12 2023-03-21 西安近代化学研究所 一种c轴取向生长的TS-1沸石单晶的合成方法
CN113368894A (zh) * 2021-06-09 2021-09-10 中国石油大学(华东) 一种膜厚可调控的核壳型ts-1钛硅分子筛膜制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002316026A (ja) * 2001-02-07 2002-10-29 Inst Fr Petrole 温度調節された結晶化による担持ゼオライト膜の調製方法
KR100789661B1 (ko) * 2007-01-05 2007-12-28 서강대학교산학협력단 기질－분자체 복합체의 제조방법
JP2008188564A (ja) * 2007-02-07 2008-08-21 National Institute Of Advanced Industrial & Technology 有機混合溶液の分離膜及びその製造方法
KR20090120846A (ko) * 2008-05-21 2009-11-25 서강대학교산학협력단 다양한 두께를 갖는 모든 ｂ-축이 기질에 대해서 수직으로배향된 ＭＦＩ형 제올라이트 박막 및 그의 제조방법

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7357836B2 (en) * 2003-03-06 2008-04-15 University Of Massachusetts Crystalline membranes
US20090000475A1 (en) * 2007-06-29 2009-01-01 Curtis Robert Fekety Zeolite membrane structures and methods of making zeolite membrane structures
US20100109201A1 (en) * 2008-10-31 2010-05-06 Molecular Imprints, Inc. Nano-Imprint Lithography Template with Ordered Pore Structure
KR101695496B1 (ko) * 2010-09-08 2017-01-11 서강대학교산학협력단 기재상에 3개의 결정축 배향이 모두 정렬된 종자 결정들을 2차 성장시켜 형성된 막

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002316026A (ja) * 2001-02-07 2002-10-29 Inst Fr Petrole 温度調節された結晶化による担持ゼオライト膜の調製方法
KR100789661B1 (ko) * 2007-01-05 2007-12-28 서강대학교산학협력단 기질－분자체 복합체의 제조방법
JP2008188564A (ja) * 2007-02-07 2008-08-21 National Institute Of Advanced Industrial & Technology 有機混合溶液の分離膜及びその製造方法
KR20090120846A (ko) * 2008-05-21 2009-11-25 서강대학교산학협력단 다양한 두께를 갖는 모든 ｂ-축이 기질에 대해서 수직으로배향된 ＭＦＩ형 제올라이트 박막 및 그의 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110882715A (zh) * 2018-09-07 2020-03-17 中国科学院大连化学物理研究所 一种分子筛催化剂的制备方法及应用
CN110882715B (zh) * 2018-09-07 2021-03-26 中国科学院大连化学物理研究所 一种乙醇与苯气相烷基化制备乙苯催化剂及其制备和应用

Also Published As

Publication number Publication date
US9938637B2 (en) 2018-04-10
US20150064440A1 (en) 2015-03-05
KR101421357B1 (ko) 2014-07-18
KR20130079288A (ko) 2013-07-10

Similar Documents

Publication Publication Date Title
WO2016085177A1 (fr) Séparateur en zéolite de type chabazite ayant une taille des pores réglée à l'aide d'un dépôt chimique en phase vapeur et son procédé de fabrication
US11554348B2 (en) Method of preparing hierarchical porous channel molecular sieve membrane and application thereof
WO2012033347A2 (fr) Film formé par des germes cristallins de croissance secondaire ayant trois axes cristallins orientés sur un substrat
US10933382B2 (en) Supported zeolite membranes
KR20070086085A (ko) 실리콘 베타 제올라이트를 함유하는 층간 유전체막의 제조방법
JP2004504716A (ja) シリカゼオライト低誘電率薄膜
WO2018110998A2 (fr) Zéolite mfi ayant une structure hiérarchique microporeuse et mésoporeuse, son procédé de préparation et son utilisation catalytique
WO2013100734A1 (fr) Procédé de fabrication d'un film de zéolite dans lequel un axe est orienté complètement verticalement, à l'aide de vapeur d'eau dans des conditions exemptes de gel synthétique
CA2108719A1 (fr) Zeolites melanges et methode pour leur production
CN107029561B (zh) 一种h0h取向的MFI型分子筛膜的制备方法
WO2018110860A1 (fr) Méthode de préparation de zéolite à l'aide d'un agent d'orientation de structure porteuse de groupes benzyle, et zéolite préparée à partir de celle-ci
CN101967230A (zh) 一种基于笼型倍半硅氧烷结构的有机/无机微孔硅及制备方法
JP2012016688A (ja) 熱亀裂が防止されたゼオライト分離膜及びその製造方法
WO2013187541A1 (fr) Substrat ayant au moins une surface partiellement ou entièrement plate, et son utilisation
CN111760467A (zh) 一种t型沸石分子筛膜的制备方法
CN1879952B (zh) 一种研磨涂覆晶种层生长制备沸石膜方法
KR20000005219A (ko) 개량된 막_
JP2001031416A (ja) ゼオライト膜の製造方法、ｍｆｉ型ゼオライト膜および分子を分離する方法
KR101637934B1 (ko) 다공성 알루미노 실리카의 제조방법 및 이에 따라 제조되는 다공성 알루미노 실리카
US8343880B2 (en) Process for preparing a dielectric interlayer film containing silicon beta zeolite
CN112705053A (zh) 一种耐酸性沸石分子筛膜的制备方法及应用
KR101128358B1 (ko) Ｌｔａ 제올라이트 분리막 및 그 제조 방법
KR20010062256A (ko) 실리카 수트의 제조공정
JP2004168615A (ja) 多孔質シリカ膜及びその製造方法
CN111013404B (zh) 一种超薄mfi分子筛膜的快速经济的合成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12861191

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 14369973

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 12861191

Country of ref document: EP

Kind code of ref document: A1